Process for preparing tertiary alkyl organic peroxides

Abstract

The present disclosure relates to a method for preparing a tertiary alkyl organic peroxide, comprising: a) reacting a component containing at least one tertiary alcohol group with a compound containing at least one tertiary hydroperoxide functional group in the presence of a catalyst and an optional co-catalyst in a first condensation step to form a mixture comprising an organic phase containing a tertiary alkyl organic peroxide and an aqueous phase; b) separating the aqueous phase from the organic phase in a dehydration step; and c) continuing to react the component containing at least one tertiary alcohol group with the compound containing at least one tertiary hydroperoxide group in the presence of a catalyst and an optional co-catalyst in a second condensation step, wherein the molar ratio between the compound containing at least one tertiary hydroperoxide functional group and the component containing at least one tertiary alcohol group in the first condensation step is at least 3:1, and no dehydration occurs during the first condensation step.

Description

[Technical Field]

[0001] The present disclosure relates to methods for preparing tertiary alkyl organic peroxides that produce lower amounts of salt waste in wastewater streams. [Background technology]

[0002] Tertiary alkyl organic peroxides are typically produced by the condensation reaction between a tertiary alcohol and a tertiary hydroperoxide. The reaction generates significant amounts of water that must be removed during the reaction. Therefore, the reaction is typically carried out in the presence of significant amounts of sulfuric acid (H2SO4) and / or with simultaneous removal of water by azeotropic distillation.

[0003] Such processes present several technical challenges. The need for large amounts of sulfuric acid results in the generation of large amounts of salt waste in the wastewater, which is undesirable (especially from an environmental perspective). Azeotropic removal of water during the reaction can be dangerous because accidentally removing too much water can lead to a runaway reaction, which is particularly dangerous when peroxides are involved. Furthermore, the reaction typically needs to be carried out at lower temperatures (e.g., below about 60°C) to avoid peroxide decomposition under these process conditions. Peroxide decomposition reduces yields and introduces additional safety issues. Lower temperatures result in slower reactions and therefore longer reaction times, which are undesirable from an industrial process perspective.

[0004] U.S. Patent No. 5,312,998 discloses a method for preparing di-tert-butyl peroxide by the condensation reaction between a substantial excess of t-butyl alcohol and t-butyl hydroperoxide in the presence of phosphotungstic acid at elevated temperatures and pressures. These are not ideal process conditions, particularly since phosphotungstic acid poses significant safety and environmental hazards and a substantial excess of tertiary alcohol is required. Tertiary alcohols are often the more expensive reagents when producing tertiary alkyl organic peroxides.

[0005] U.S. Patent No. 3,308,163 discloses a method for preparing organic peroxides by the condensation reaction between an organic alcohol and an organic hydroperoxide in the presence of an acidic solid ion exchange resin. The azeotropic removal of water during the condensation reaction is shown to be essential to the method.

[0006] U.S. Patent No. 3,919,326 discloses a method for preparing organic peroxides by the condensation reaction between a poly(hydroxyisopropyl) aryl compound containing at least two alpha-hydroxyisopropyl groups and a chemically equivalent amount of t-alkyl hydroperoxide in the presence of p-toluenesulfonic acid and a large amount of organic solvent. The method required azeotropic removal of water during the condensation reaction, and even at elevated process temperatures of 70-80°C, the reaction was still relatively slow (>3.5 hours to completion).

[0007] European Patent No. 0967194 discloses a process for preparing dicumyl peroxide by the condensation reaction between cumyl alcohol and cumene hydroperoxide in the presence of an aromatic sulfonic acid. The process disclosed therein resulted in unimpressive product yields (<80%).

[0008] U.S. Patent Application Publication No. 2016207882 discloses a method for preparing tertiary alkyl organic peroxides by the condensation reaction between a tertiary organic alcohol and a tertiary organic hydroperoxide in the presence of sulfonic acid and sulfuric acid, where the molar ratio of sulfonic acid to tertiary alcohol is 0.1 to 0.6. Worked examples of the pathway-determining method in U.S. Patent Application Publication No. 016207882 indicate that substantial amounts of sulfuric acid are required (>60 mol% relative to the molar amount of organic alcohol), which may explain why the method required multiple aqueous wash steps of the final organic layer (presumably to remove substantial amounts of acidic waste salts) and did not consistently result in good product yields.

[0009] There remains a need for a process for preparing tertiary alkyl organic peroxides that addresses all of the technical problems discussed above. Summary of the Invention

[0010] The present inventors have now developed a highly effective method for producing tertiary alkyl organic peroxides that addresses all of the technical problems mentioned above.

[0011] In that regard, in a first aspect, the present invention relates to a method for preparing a tertiary alkyl organic peroxide, comprising: a) in a first condensation step, reacting a component containing at least one tertiary alcohol group with a compound containing at least one tertiary hydroperoxide functional group in the presence of a catalyst and an optional co-catalyst to form a mixture comprising an organic phase containing a tertiary alkyl organic peroxide and an aqueous phase; b) separating the aqueous phase from the organic phase in a dehydration step; c) continuing to react the component containing at least one tertiary alcohol group with the compound containing at least one tertiary hydroperoxide group in the presence of a catalyst and an optional co-catalyst in a second condensation step; In the first condensation step, the molar ratio between the compound containing at least one tertiary hydroperoxide functional group and the component containing at least one tertiary alcohol group is at least 3:1; and No dehydration is carried out during the first condensation step.

[0012] An unexpected discovery was that the introduction of an intermediate dehydration step during the reaction eliminated the need for azeotropic dehydration during the first condensation step, allowing for an increase in reaction temperature (thus reducing overall reaction time), which significantly reduced the overall amount of catalyst required (thereby substantially reducing the amount of salt waste produced), without sacrificing product yield (>90%) and maintaining very high selectivity to the desired product. However, to ensure these benefits, it was found that the molar ratio between the compound containing at least one tertiary hydroperoxide functional group and the component containing at least one tertiary alcohol group needed to be at least 3:1. This ratio was found to be critical to the success of the process: below this 3:1 ratio, the resulting suspension was very viscous, making stirring very difficult, and the mixture contained undissolved tertiary alcohol, which caused fouling on the reactor walls and reduced reaction rates, i.e., led to long reaction times. It was also found that the selectivity of the reaction could be improved by increasing the molar ratio. Therefore, it is preferred if the molar ratio between the compound containing at least one tertiary hydroperoxide functional group and the component containing at least one tertiary alcohol group is greater than 3:1, preferably at least 3.5:1, and more preferably at least 4:1.

[0013] For the avoidance of doubt, it should be understood that in the intermediate dehydration step b), the organic and aqueous phases of step a) are allowed to settle / separate (typically by ceasing stirring / agitation) and the separated aqueous layer is then removed.

[0014] Preferably, the component containing at least one tertiary alcohol group and / or the compound containing at least one tertiary hydroperoxide functional group contains one or more aromatic functional groups, such that the tertiary alkyl organic peroxide contains at least one aromatic functional group.

[0015] Preferably, the component containing at least one tertiary alcohol group is selected from α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or mixtures thereof.

[0016] Preferably, the compound containing at least one tertiary hydroperoxide group is selected from tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, isopropylcumyl hydroperoxide, pinane hydroperoxide (2,6,6-trimethylbicyclo[3.1.1]heptyl hydroperoxide), para-menthane hydroperoxide, and mixtures thereof, with tert-butyl hydroperoxide being most preferred.

[0017] Preferably, the catalyst is an acid catalyst, preferably selected from aliphatic sulfonic acids, aromatic sulfonic acids, and / or perchloric acid. Preferred sulfonic acids include, but are not limited to, para-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, 1,5-naphthalenedisulfonic acid, ethanesulfonic acid, and mixtures thereof. Para-toluenesulfonic acid (PTSA) is most preferred.

[0018] The method may use a cocatalyst in the first and / or second condensation steps. Preferred cocatalysts include, but are not limited to, at least one water-soluble salt of an inorganic acid. Preferred water-soluble inorganic acid salts include, but are not limited to, perchlorates, sulfates, perborates, and mixtures thereof. The cation counterion of the inorganic acid salt is preferably an alkali metal cation, preferably sodium, potassium, magnesium, or calcium. More preferred cocatalysts include sodium perchlorate, potassium sulfate, potassium perchlorate, magnesium sulfate, sodium perchlorate, magnesium sulfate, and mixtures thereof. Sodium perchlorate is most preferred.

[0019] Thus, in a preferred embodiment, the method for preparing a tertiary alkyl organic peroxide comprises: a) in a first condensation step, reacting α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof with tert-butyl hydroperoxide in the presence of a catalyst (preferably para-toluenesulfonic acid) and an optional co-catalyst (preferably sodium perchlorate) to form a mixture comprising an organic phase containing a tertiary alkyl organic peroxide and an aqueous phase; b) separating the aqueous phase from the organic phase in a dehydration step; c) in a second condensation step, continuing to react α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof with tert-butyl hydroperoxide in the presence of a catalyst (preferably para-toluenesulfonic acid) and an optional co-catalyst (preferably sodium perchlorate); In the first condensation step, the molar ratio between tert-butyl hydroperoxide and α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof is at least 3:1; and No dehydration occurs during the first condensation step.

[0020] Preferably, the first portion of catalyst and optional cocatalyst are added in the first condensation stage, and the second portion of catalyst and optional cocatalyst are added in the second condensation stage. Preferably, the first portion of catalyst is added in an amount of 3 to 15 mol%, preferably 4 to 10 mol%, (relative to the initial moles of components containing at least one tertiary alcohol group) in the first condensation stage, and the second portion of catalyst is added in an amount of 3 to 15 mol%, preferably 4 to 10 mol%, (relative to the initial moles of components containing at least one tertiary alcohol group) in the second condensation stage. When a cocatalyst is used, it is preferred if the first portion of cocatalyst is added in an amount of 2 to 10 mol%, preferably 3 to 8 mol%, (relative to the initial moles of components containing at least one tertiary alcohol group) in the first condensation stage, and the second portion of cocatalyst is added in an amount of 2 to 10 mol%, preferably 3 to 8 mol%, (relative to the initial moles of components containing at least one tertiary alcohol group) in the second condensation stage. It should be understood that the catalyst / optional cocatalyst in the first portion need not be in the same amount as the catalyst / optional cocatalyst in the second portion.

[0021] Thus, in another preferred embodiment, the method for preparing a tertiary alkyl organic peroxide comprises: a) in a first condensation step, reacting a component containing at least one tertiary alcohol group with a compound containing at least one tertiary hydroperoxide functional group in the presence of 3 to 15 mol % of a catalyst (based on the initial moles of the component containing at least one tertiary alcohol group) and optionally 2 to 10 mol % of a cocatalyst (based on the initial moles of the component containing at least one tertiary alcohol group) to form a mixture comprising an organic phase containing a tertiary alkyl organic peroxide and an aqueous phase; b) separating the aqueous phase from the organic phase in a dehydration step; c) in a second condensation step, continuing to react the component containing at least one tertiary alcohol group with the compound containing at least one tertiary hydroperoxide group in the presence of 3 to 15 mol % of catalyst (relative to the initial number of moles of the component containing at least one tertiary alcohol group) and optionally 2 to 10 mol % of co-catalyst (relative to the initial number of moles of the component containing at least one tertiary alcohol group), In the first condensation step, the molar ratio between the compound containing at least one tertiary hydroperoxide functional group and the component containing at least one tertiary alcohol group is at least 3:1; and No dehydration occurs during the first condensation step.

[0022] In a more preferred embodiment, the method for preparing a tertiary alkyl organic peroxide comprises: a) in a first condensation step, reacting α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof with tert-butyl hydroperoxide in the presence of 3 to 15 mol % of a catalyst (preferably para-toluenesulfonic acid; mol % relative to the initial number of moles of components containing at least one tertiary alcohol group) and optional 2 to 10 mol % of a co-catalyst (preferably sodium perchlorate; mol % relative to the initial number of moles of components containing at least one tertiary alcohol group) to form a mixture comprising an organic phase containing a tertiary alkyl organic peroxide and an aqueous phase; b) separating the aqueous phase from the organic phase in a dehydration step; c) in a second condensation step, continuing to react α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof with tert-butyl hydroperoxide in the presence of 3 to 15 mol % of a catalyst (preferably para-toluenesulfonic acid; mol % relative to the initial number of moles of the component containing at least one tertiary alcohol group) and optional 2 to 10 mol % of a co-catalyst (preferably sodium perchlorate; mol % relative to the initial number of moles of the component containing at least one tertiary alcohol group), wherein the molar ratio between tert-butyl hydroperoxide and α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof is at least 3:1; and No dehydration occurs during the first condensation step.

[0023] As mentioned above, the process conditions allow for higher reaction temperatures. The optimum process temperature for the first and / or second condensation steps has been found to be 55-80°C, preferably 62-80°C, preferably 65-80°C, preferably 67-80°C, more preferably 69-80°C. The dehydration step b) may be carried out at a lower temperature than the first and / or second condensation steps (e.g., at about 50-60°C).

[0024] It has also been found that, although organic solvents may be used in the methods disclosed herein, they are not essential for the success of the methods disclosed herein. Thus, the first and / or second condensation step reactions may be carried out in the absence of organic solvents. This is beneficial from the standpoint of process cost and safety, and substantially improves the environmental profile of the method.

[0025] As noted above, it is essential that the molar ratio between the compound containing at least one tertiary hydroperoxide functional group and the component containing at least one tertiary alcohol group be at least 3:1 (i.e., the hydroperoxide is present in excess). Thus, to improve the overall efficiency of the process, it is preferred if the process further comprises recycling at least a portion of the compound containing at least one tertiary hydroperoxide group present in the product of the second condensation step to the first condensation step.

[0026] Thus, in another preferred embodiment, the method for preparing a tertiary alkyl organic peroxide comprises: a) in a first condensation step, reacting a component containing at least one tertiary alcohol group with a compound containing at least one tertiary hydroperoxide functional group in the presence of a catalyst and an optional co-catalyst to form a mixture comprising an organic phase containing a tertiary alkyl organic peroxide and an aqueous phase; b) separating the aqueous phase from the organic phase in a dehydration step; c) continuing to react the component containing at least one tertiary alcohol group with the compound containing at least one tertiary hydroperoxide group in the presence of a catalyst in a second condensation step; in the first condensation step, the molar ratio between the compound containing at least one tertiary hydroperoxide functional group and the component containing at least one tertiary alcohol group is at least 3:1; No dehydration is carried out during the first condensation step, and At least a portion of the compound containing at least one tertiary hydroperoxide group present in the product of the second condensation stage is recycled to the first condensation stage.

[0027] In a more preferred embodiment, the method for preparing a tertiary alkyl organic peroxide comprises: a) in a first condensation step, reacting α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof with tert-butyl hydroperoxide in the presence of 3 to 15 mol % of a catalyst (preferably para-toluenesulfonic acid; mol % relative to the initial number of moles of components containing at least one tertiary alcohol group) and optional 2 to 10 mol % of a co-catalyst (preferably sodium perchlorate; mol % relative to the initial number of moles of components containing at least one tertiary alcohol group) to form a mixture comprising an organic phase containing a tertiary alkyl organic peroxide and an aqueous phase; b) separating the aqueous phase from the organic phase in a dehydration step; c) in a second condensation step, continuing to react α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof with tert-butyl hydroperoxide in the presence of 3 to 15 mol % of a catalyst (preferably para-toluenesulfonic acid; mol % relative to the initial number of moles of the component containing at least one tertiary alcohol group) and optional 2 to 10 mol % of a co-catalyst (preferably sodium perchlorate; mol % relative to the initial number of moles of the component containing at least one tertiary alcohol group), wherein the molar ratio between tert-butyl hydroperoxide and α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof is at least 3:1; No dehydration is carried out during the first condensation step, and At least a portion of the tert-butyl hydroperoxide present in the product of the second condensation stage is recycled to the first condensation stage.

[0028] The methods disclosed herein may be carried out as a batch process or in a continuous manner.

[0029] It should be noted that various elements of the present invention, including but not limited to the preferred ranges of various parameters, can be combined unless they are mutually exclusive.

[0030] The present invention is illustrated by, but not limited to, or by, the following examples. [Example]

[0031] Example 1 (molar ratio t-OOH:t-OH=4.1:1) A 1 L glass reactor equipped with a bottom valve, mechanical stirrer, thermometer, and reflux condenser was charged with 342.9 g (2.66 mol) of TBHP as a 70 wt% aqueous solution. 126.2 g (0.65 mol) of α,α'-dihydroxy-1,3-diisopropylbenzene and 6.63 g (0.032 mol) of a 60 wt% aqueous solution of sodium perchlorate were then added, and the mixture was heated to 62.5 °C. Within 5 minutes, 9.51 g (0.036 mol) of a 65 wt% aqueous solution of p-toluenesulfonic acid was added to the mixture. After 20 minutes, the temperature was reduced to 60 °C. Stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0032] Stirring was started, 6.63 g (0.032 mol) of a 60 wt. % aqueous solution of sodium perchlorate was added, and the mixture was heated to 62.5° C. Within 5 minutes, 9.51 g (0.036 mol) of a 65 wt. % aqueous solution of p-toluenesulfonic acid was added to the mixture. The mixture was stirred for 100 minutes and then cooled to 60° C. Stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0033] The amount of catalyst (PTSA) added (relative to the initial moles of components containing at least one tertiary alcohol group): 5.5 mol% ((0.036 / 0.65)*100) in the first condensation step; 5.5 mol% in the second condensation step; a total of 11 mol%.

[0034] The amount of co-catalyst (NaClO4) added (relative to the initial moles of components containing at least one tertiary alcohol group): 5 mol% ((0.032 / 0.60)*100) in the first condensation step; 5 mol% in the second condensation step; a total of 10 mol%.

[0035] GC analysis of the organic phase excluding TBHP showed the following composition: 95.53% α,α′-bis-( tert -butylperoxy)-1,3-diisopropylbenzene, 0.76% α-( tert -butylperoxy)-α′-hydroxy-1,3-diisopropylbenzene, and 2.53% α-( tert -butylperoxy)isopropyl-3-isopropenylbenzene.

[0036] Example 2 (molar ratio of t-OOH:t-OH=4.1:1) A 1 L glass reactor equipped with a bottom valve, mechanical stirrer, thermometer, and reflux condenser was charged with 171.7 g of TBHP as a 70 wt % aqueous solution. After adding 63.2 g of α,α'-dihydroxy-1,3-diisopropylbenzene and 3.32 g of a 60 wt % aqueous solution of sodium perchlorate, the mixture was heated to 62.5 °C. Within 5 minutes, 4.76 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. After 20 minutes, the temperature was reduced to 60 °C. The stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0037] Stirring was started, 3.32 g of a 60 wt % aqueous solution of sodium perchlorate was added, and the mixture was heated to 62.5° C. Within 5 minutes, 9.52 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. The mixture was stirred for 80 minutes and then cooled to 60° C. Stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0038] Amount of catalyst (PTSA) added (relative to the initial number of moles of components containing at least one tertiary alcohol group): 5 mol% in the first condensation step; 10 mol% in the second condensation step; 15 mol% in total.

[0039] Amount of cocatalyst (NaClO4) added (relative to the initial moles of components containing at least one tertiary alcohol group): 5 mol% in the first condensation step; 5 mol% in the second condensation step; 10 mol% in total.

[0040] GC analysis of the organic phase excluding TBHP showed the following composition: 95.91% α,α′-bis-( tert -butylperoxy)-1,3-diisopropylbenzene, 0.50% α-( tert -butylperoxy)-α′-hydroxy-1,3-diisopropylbenzene, and 2.51% α-( tert -butylperoxy)isopropyl-3-isopropenylbenzene.

[0041] Example 3 (molar ratio of t-OOH:t-OH=4.1:1) A 1 L glass reactor equipped with a bottom valve, mechanical stirrer, thermometer, and reflux condenser was charged with 172.26 g of TBHP as a 70 wt % aqueous solution. After adding 63.4 g of α,α'-dihydroxy-1,3-diisopropylbenzene and 3.33 g of a 60 wt % aqueous solution of sodium perchlorate, the mixture was heated to 67.5 °C. Within 5 minutes, 4.78 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. After 20 minutes, the temperature was reduced to 60 °C. The stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0042] Stirring was started, 3.33 g of a 60 wt % aqueous solution of sodium perchlorate was added, and the mixture was heated to 67.5° C. Within 5 minutes, 5.73 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. The mixture was stirred for 20 minutes and then cooled to 60° C. Stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0043] Amount of catalyst (PTSA) added (relative to the initial number of moles of components containing at least one tertiary alcohol group): 6 mol% in the first condensation step; 7 mol% in the second condensation step; 13 mol% in total.

[0044] Amount of cocatalyst (NaClO4) added (relative to the initial moles of components containing at least one tertiary alcohol group): 5 mol% in the first condensation step; 5 mol% in the second condensation step; 10 mol% in total.

[0045] GC analysis of the organic phase excluding TBHP showed the following composition: 95.22% α,α′-bis-( tert -butylperoxy)-1,3-diisopropylbenzene, 0.39% α-( tert -butylperoxy)-α′-hydroxy-1,3-diisopropylbenzene, and 2.17% α-( tert -butylperoxy)isopropyl-3-isopropenylbenzene.

[0046] Example 4 (molar ratio t-OOH:t-OH=3:1) A 1 L glass reactor equipped with a bottom valve, mechanical stirrer, thermometer, and reflux condenser was charged with 163.09 g of TBHP as a 70 wt % aqueous solution. After adding 80.0 g of α,α'-dihydroxy-1,3-diisopropylbenzene and 4.21 g of a 60 wt % aqueous solution of sodium perchlorate, the mixture was heated to 67.5 °C. Within 5 minutes, 4.72 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. After 60 minutes, the temperature was reduced to 60 °C. The stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0047] Stirring was started, 4.21 g of a 60 wt % aqueous solution of sodium perchlorate was added, and the mixture was heated to 67.5° C. Within 5 minutes, 4.72 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. The mixture was stirred for 240 minutes and then cooled to 60° C. Stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0048] Amount of catalyst (PTSA) added (relative to the initial number of moles of components containing at least one tertiary alcohol group): 4.3 mol% in the first condensation step; 4.3 mol% in the second condensation step; 8.6 mol% in total.

[0049] Amount of cocatalyst (NaClO4) added (relative to the initial moles of components containing at least one tertiary alcohol group): 5 mol% in the first condensation step; 5 mol% in the second condensation step; 10 mol% in total.

[0050] GC analysis of the organic phase excluding TBHP showed the following composition: 92.25% α,α′-bis-( tert -butylperoxy)-1,3-diisopropylbenzene, 2.17% α-( tert -butylperoxy)-α′-hydroxy-1,3-diisopropylbenzene, and 4.01% α-( tert -butylperoxy)isopropyl-3-isopropenylbenzene.

[0051] Example 5 (molar ratio of t-OOH:t-OH=4.1:1) A 1 L glass reactor equipped with a bottom valve, mechanical stirrer, thermometer, and reflux condenser was charged with 217.36 g of TBHP as a 70 wt % aqueous solution. After adding 80.0 g of α,α'-dihydroxy-1,3-diisopropylbenzene and 4.20 g of a 60 wt % aqueous solution of sodium perchlorate, the mixture was heated to 69.5 °C. Within 5 minutes, 4.72 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. After 20 minutes, the temperature was reduced to 60 °C. The stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0052] Stirring was started, 4.20 g of a 60 wt % aqueous solution of sodium perchlorate was added, and the mixture was heated to 69.5° C. Within 5 minutes, 4.72 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. The mixture was stirred for 60 minutes and then cooled to 60° C. Stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0053] Amount of catalyst (PTSA) added (relative to the initial number of moles of components containing at least one tertiary alcohol group): 4.3 mol% in the first condensation step; 4.3 mol% in the second condensation step; 8.6 mol% in total.

[0054] Amount of cocatalyst (NaClO4) added (relative to the initial moles of components containing at least one tertiary alcohol group): 5 mol% in the first condensation step; 5 mol% in the second condensation step; 10 mol% in total.

[0055] GC analysis of the organic phase excluding TBHP showed the following composition: 94.72% α,α′-bis-( tert -butylperoxy)-1,3-diisopropylbenzene, 0.83% α-( tert -butylperoxy)-α′-hydroxy-1,3-diisopropylbenzene, and 3.04% α-( tert -butylperoxy)isopropyl-3-isopropenylbenzene.

[0056] Example 6 (molar ratio of t-OOH:t-OH=4.1:1) A 1 L glass reactor equipped with a bottom valve, mechanical stirrer, thermometer, and reflux condenser was charged with 244.5 g of TBHP as a 70 wt % aqueous solution. After adding 90.0 g of α,α'-dihydroxy-1,3-diisopropylbenzene and 2.70 g of solid sodium perchlorate, the mixture was heated to 69.5 °C. Within 5 minutes, 5.31 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. After 20 minutes, the temperature was reduced to 60 °C. The stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0057] Stirring was started, 2.70 g of solid sodium perchlorate was added, and the mixture was heated to 69.5° C. Within 5 minutes, 5.31 g of a 65 wt % aqueous solution of p-toluenesulfonic acid was added to the mixture. The mixture was stirred for 50 minutes and then cooled to 60° C. Stirring was stopped, and the aqueous phase was removed via the bottom valve.

[0058] Amount of catalyst (PTSA) added (relative to the initial number of moles of components containing at least one tertiary alcohol group): 4.3 mol% in the first condensation step; 4.3 mol% in the second condensation step; 8.6 mol% in total.

[0059] Amount of cocatalyst (NaClO4) added (relative to the initial moles of components containing at least one tertiary alcohol group): 5 mol% in the first condensation step; 5 mol% in the second condensation step; 10 mol% in total.

[0060] GC analysis of the organic phase excluding TBHP showed the following composition: 94.82% α,α′-bis-( tert -butylperoxy)-1,3-diisopropylbenzene, 1.41% α-( tert -butylperoxy)-α′-hydroxy-1,3-diisopropylbenzene, and 2.52% α-( tert -butylperoxy)isopropyl-3-isopropenylbenzene.

[0061] As used herein, unless expressly indicated otherwise, the word "or" is used to mean an operator that returns a true value when either or both stated conditions are met, as opposed to the operator "exclusive or," which requires that only one of the stated conditions be met. The word "comprising" is used in the sense of "including," not "consisting of." All prior teachings identified above are incorporated herein by reference. Admission of any prior-published document herein should not be construed as an admission or representation that its teachings were general knowledge in Europe or elsewhere as of the date hereof.

Claims

1. 1. A process for preparing a tertiary alkyl organic peroxide, comprising: a) in a first condensation step, reacting a component containing at least one tertiary alcohol group with a compound containing at least one tertiary hydroperoxide functional group in the presence of a catalyst and an optional co-catalyst to form a mixture comprising an organic phase containing a tertiary alkyl organic peroxide and an aqueous phase; b) separating the aqueous phase from the organic phase in a dehydration step; c) continuing to react the component containing at least one tertiary alcohol group with the compound containing at least one tertiary hydroperoxide group in the presence of a catalyst and an optional co-catalyst in a second condensation step; In the first condensation step, the molar ratio between the compound containing at least one tertiary hydroperoxide functional group and the component containing at least one tertiary alcohol group is at least 3:1; and A process wherein no dehydration is carried out during said first condensation step.

2. 10. The method of claim 1, wherein the component and / or compound contains one or more aromatic functional groups such that the tertiary alkyl organic peroxide contains at least one aromatic functional group.

3. 3. The method of claim 1 or claim 2, wherein the component containing at least one tertiary alcohol group is selected from α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof.

4. 4. The method of claim 1, wherein the compound containing at least one tertiary hydroperoxide group is selected from tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, isopropylcumyl hydroperoxide, pinane hydroperoxide (2,6,6-trimethylbicyclo[3.1.1]heptyl hydroperoxide), para-menthane hydroperoxide, or a mixture thereof.

5. 5. The process according to any one of claims 1 to 4, wherein the reaction of the first and / or second condensation step is carried out in the absence of an organic solvent.

6. The process according to any one of claims 1 to 5, wherein the catalyst is an acid catalyst, preferably selected from aliphatic sulfonic acids, aromatic sulfonic acids, and / or perchloric acid.

7. 7. The process according to claim 1, wherein the catalyst is added in the first and / or second condensation step in an amount of 3 mol % to 15 mol % relative to the initial number of moles of components containing at least one tertiary alcohol group.

8. 8. The method of claim 7, wherein a first portion of catalyst is added in the first condensation step in an amount of 3 mol % to 15 mol % based on the initial number of moles of components containing at least one tertiary alcohol group, and a second portion of catalyst is added in the second condensation step in an amount of 3 mol % to 15 mol % based on the initial number of moles of components containing at least one tertiary alcohol group.

9. 9. The process according to any one of claims 1 to 8, wherein the first and second condensation steps are carried out at a temperature of from 55°C to 80°C, preferably from 62°C to 80°C, preferably from 65°C to 80°C, preferably from 67°C to 80°C, more preferably from 69°C to 80°C.

10. 10. The process according to any one of claims 1 to 9, wherein the reaction of the first and / or second condensation step is carried out in the presence of a co-catalyst.

11. 11. The process of claim 10, wherein the co-catalyst is added in the first and / or second condensation step in an amount of 2 mol % to 10 mol % relative to the initial number of moles of component containing at least one tertiary alcohol group.

12. 12. The method of claim 11, wherein a first portion of co-catalyst is added in the first condensation step in an amount of 2 mol % to 10 mol % based on the initial number of moles of components containing at least one tertiary alcohol group, and a second portion of co-catalyst is added in the second condensation step in an amount of 2 mol % to 10 mol % based on the initial number of moles of components containing at least one tertiary alcohol group.

13. 13. The method of any one of claims 1 to 12, wherein the catalyst is para-toluenesulfonic acid and the co-catalyst is sodium perchlorate.

14. 14. The method of any one of claims 1 to 13, wherein the component containing at least one tertiary alcohol group is selected from α,α'-dihydroxy-1,3-diisopropylbenzene, α,α'-dihydroxy-1,4-diisopropylbenzene, or a mixture thereof, and the compound containing at least one tertiary hydroperoxide group is tert-butyl hydroperoxide.

15. 15. The process of any one of claims 1 to 14, further comprising recycling at least a portion of the compound containing at least one tertiary hydroperoxide group present in the product of the second condensation step to the first condensation step.

Images